Biomimetic bacterial photosynthetic reaction center complexes have been constructed using welldefined self-assembled supramolecular approaches. The “special pair” donor, a cofacial phthalocyanine dimer, was formed via potassium ion induced dimerization of tetra-(benzo-[15]crown-5) phthalocyanine. The dimer was subsequently self-assembled with functionalized fullerene(s) via axial coordination. The utilization of such welldefined multiple modes of binding in a controlled fashion results in the formation biomimetic supramolecualr complexes which further allows to probe the photoinduced charge separation. These complexes were fully characterized using 1H NMR, UV-Vis, electrochemical and mass spectrometric methods. The evidence for interaction in the ground state systems was obtained from spectroscopic and computational studies. Electron transfer from the excited zinc phthalocyanine to fullerene was reveled by steady and time-resolved emission studies.